James E. Brady The Molecular Nature of Matter (6th Edition) Copia PDF

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This page intentionally left blank Sixth Edition Chemistry The Molecular Nature of Matter jespe_fm-hr.indd 1 11/30/10 1:05 PM This page intentionally left blank Sixth Edition Chemistry The Molecular Nature of Matter Neil D. Jespersen St. John’s University, New York James E. Brady St. John’s Univers...

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Sixth Edition

Chemistry The Molecular Nature of Matter

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Sixth Edition

Chemistry The Molecular Nature of Matter

Neil D. Jespersen St. John’s University, New York

James E. Brady St. John’s University, New York In collaboration with

Alison Hyslop

St. John’s University, New York

John Wiley and Sons, Inc.

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VICE PRESIDENT, EXECUTIVE PUBLISHER ASSOCIATE PUBLISHER ACQUISITION EDITOR PROJECT EDITOR MARKETING MANAGER SENIOR DESIGNER INTERIOR DESIGNER SENIOR ILLUSTRATION EDITOR SENIOR PHOTO EDITOR PHOTO RESEARCHER EXECUTIVE MEDIA EDITOR MEDIA EDITOR MEDIA PRODUCTION EDITOR CONTENT MANAGER COVER PHOTO

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This book was set in 10.5 Adobe Garamond by Prepare and printed and bound by Courier Kendallville. The cover was printed by Courier Kendallville. This book is printed on acid free paper. ∞ Founded in 1807, John Wiley & Sons, Inc. has been a valued source of knowledge and understanding for more than 200 years, helping people around the world meet their needs and fulfill their aspirations. Our company is built on a foundation of principles that include responsibility to the communities we serve and where we live and work. In 2008, we launched a Corporate Citizenship Initiative, a global effort to address the environmental, social, economic, and ethical challenges we face in our business. Among the issues we are addressing are carbon impact, paper specifications and procurement, ethical conduct within our business and among our vendors, and community and charitable support. For more information, please visit our website: www.wiley.com/go/citizenship. Copyright © 2012, 2009, 2004, 2000 John Wiley & Sons, Inc. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc. 222 Rosewood Drive, Danvers, MA 01923, website www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030-5774, (201)748-6011, fax (201)748-6008, website http://www.wiley.com/go/permissions. Evaluation copies are provided to qualified academics and professionals for review purposes only, for use in their courses during the next academic year. These copies are licensed and may not be sold or transferred to a third party. Upon completion of the review period, please return the evaluation copy to Wiley. Return instructions and a free of charge return shipping label are available at www.wiley.com/go/returnlabel. Outside of the United States, please contact your local representative. Library of Congress Cataloging-in-Publication Data Jespersen, Neil D. Chemistry: the molecular nature of matter/Neil D. Jespersen, James E. Brady; In collaboration with Alison Hyslop. – 6th ed. p. cm. Previous edition: Chemistry/James E. Brady, Fred Senese; in collaboration with Neil D. Jespersen. Includes index. ISBN 978-0-470-57771-4 (cloth) Binder-Ready Version ISBN 978-0-470-91770-1 1. Chemistry. I. Jespersen, Neil D. II. Brady, James E. III. Hyslop, Alison IV. Title. QD33.2.B73 2012 540–dc22

2010043302

Printed in the United States of America 10 9 8 7 6 5 4 3 2 1

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About the Authors Neil D. Jespersen is a Professor of Chemistry at St. John’s University in New York. He earned a B.S. with Special Attainments in Chemistry at Washington and Lee University (VA) and his Ph.D. in Analytical Chemistry with Joseph Jordan at The Pennsylvania State University. He has received awards for excellence in teaching and research from St. John’s University and the E. Emmit Reid Award in college teaching from the American Chemical Society’s Middle Atlantic Region. He chaired the Department of Chemistry for 6 years and has mentored the St. John’s student ACS club for over 30 years while continuing to enjoy teaching Quantitative and Instrumental Analysis courses, along with General Chemistry. He has been an active contributor to the Eastern Analytical Symposium, chairing it in 1991. Neil has authored the Barrons AP Chemistry Study Guide; has edited 2 books on Instrumental Analysis and Thermal Analysis; and has 4 chapters in research monographs, 50 refereed publications, and 150 abstracts and presentations. He is active at the local, regional and national levels of the American Chemical Society, and was recently elected to the ACS Board of Directors. When there is free time you can find him playing tennis, baseball with four grandchildren, or traveling with his wife Marilyn. James E. Brady received his BA degree from Hofstra College in 1959 and his Ph.D. from Penn State University under the direction of C. David Schmulbach in 1963. He is Professor Emeritus at St. John’s University, New York, where he taught graduate and undergraduate courses for 35 years. His first textbook, General Chemistry: Principles and Structure, coauthored with Gerard Humiston, was published in 1975. An innovative feature of the text was 3D illustrations of molecules and crystal structures that could be studied with a stereo viewer that came tucked into a pocket inside the rear cover of the book. The popularity of his approach to teaching general chemistry is evident in the way his books have shaped the evolution of textbooks over the last 35 years. His useful chemical tools approach toward teaching problem solving was introduced by him at the 12th Biennial Conference on Chemical Education at UC Davis in 1992 and continues to evolve. He has been the principal coauthor of various versions of this text, along with John Holum, Joel Russell, Fred Senese, and Neil Jespersen. He is particularly pleased to be a member of the current author team. In 1999, Jim retired from St. John’s University to devote more time to writing, and since then he has coauthored three editions of this text. He and his wife, June, enjoy their current home in Jacksonville, Florida. Jim is an avid photographer and many of his photos of surfers have been published in the local newspaper. Alison Hyslop received her BA degree from Macalester College in 1986 and her Ph.D. from the University of Pennsylvania under the direction of Michael J. Therien in 1998. She is an Associate Professor at St. John’s University, New York, where she has been teaching graduate and undergraduate courses since 2000. She was a visiting Assistant Professor at Trinity College (CT) from 1998 to 1999. She was a visiting scholar at Columbia University (NY) in 2005 and in 2007 and at Brooklyn College in 2009, where she worked on research projects in the laboratory of Brian Gibney. Her research focuses on the synthesis and study of porphyrin-based light harvesting compounds. When not in the laboratory, she likes to hike in upstate New York, and practice tae kwon do.

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Brief Contents 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

| Chemistry and the Atomic/Molecular View of Matter | Scientific Measurements

29

| Elements, Compounds, and the Periodic Table | The Mole and Stoichiometry

63

106

| Molecular View of Reactions in Aqueous Solutions | Oxidation–Reduction Reactions | Energy and Chemical Change

155

213 253

| The Quantum Mechanical Atom

305

| The Basics of Chemical Bonding

357

| Theories of Bonding and Structure | Properties of Gases

1

408

472

| Intermolecular Attractions and the Properties of Liquids and Solids | Mixtures at the Molecular Level: Properties of Solutions | Chemical Kinetics

585

636

| Chemical Equilibrium

695

| Acids and Bases, A Molecular Look

740

| Acid–Base Equilibria in Aqueous Solutions | Solubility and Simultaneous Equilibria | Thermodynamics

869

| Electrochemistry

918

773

830

| Nuclear Reactions and Their Role in Chemistry | Metal Complexes

527

976

1016

| Organic Compounds, Polymers, and Biochemicals

1047

Appendix A: Review of Mathematics A-1 Appendix B: Answers to Practice Exercises and Selected Review Problems A-15 Appendix C: Tables of Selected Data A-39 Glossary G-1 Index I-1 | vii

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Table of Contents 1 | Chemistry and the Atomic/Molecular View of Matter 1.1 1.2 1.3 1.4 1.5 1.6

1

Chemistry and Its Place among the Sciences 2 Laws and Theories: The Scientific Method 3 Matter and Its Classifications 5 Dalton and the Atomic Theory 9 Atoms and Molecules and Chemical Formulas

Chemical Reactions and Chemical Equations 19

Tools for Problem Solving

24

Review Questions and Problems

24

2 | Scientific Measurements 2.1 2.2 2.3 2.4 2.5

10

29

Physical and Chemical Properties 30 Measurement of Physical and Chemical Properties 32 The Uncertainty of Measurements 41 Dimensional Analysis 45 Density and Specific Gravity 51

Tools for Problem Solving 56 Review Questions and Problems 58

3 | Elements, Compounds, and the Periodic Table 3.1 3.2 3.3 3.4 3.5 3.6 3.7

63

Internal Structure of the Atom 64 The Periodic Table

72

Metals, Nonmetals, and Metalloids 75 Ionic Compounds 78 Nomenclature of Ionic Compounds 85 Molecular Compounds

90

Nomenclature of Molecular Compounds 94

Tools for Problem Solving 98 Review Questions and Problems 100

4 | The Mole and Stoichiometry

106

4.1 The Molecular Scale versus the Laboratory Scale 4.2 Chemical Formulas and Stoichiometry 113

107

| ix

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x | Contents

4.3 Determining Empirical and Molecular Formulas 4.4 The Mole and Chemical Reactions 128 4.5 Limiting Reactants 135 4.6 Theoretical Yield and Percentage Yield 139

119

Tools for Problem Solving 143 Review Questions and Problems

144

Bringing It Together: Chapters 1–4 153

5 | Molecular View of Reactions in Aqueous Solutions 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8

155

Describing Solutions 156 Electrolytes, Weak Electrolytes, and Nonelectrolytes 157 Acids and Bases 164 Acid-Base Nomenclature 173 Double-Replacement (Metathesis) Reactions 175 Molarity

185

Solution Stoichiometry 190 Titrations and Chemical Analysis

196

Tools for Problem Solving 204 Review Questions and Problems 206

6 | Oxidation–Reduction Reactions 6.1 6.2 6.3 6.4 6.5 6.6

213

Oxidation–Reduction Reactions 214 Balancing Redox Equations 222 Acids as Oxidizing Agents 227 Redox Reactions of Metals 231 Molecular Oxygen as an Oxidizing Agent 235 Stoichiometry of Redox Reactions

239

Tools for Problem Solving 243 Review Questions and Problems 244

7 | Energy and Chemical Change 7.1 Energy: The Ability to Do Work 7.2 Internal Energy 257 7.3 Measuring Heat 259

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253

254

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Contents | xi

7.4 7.5 7.6 7.7 7.8 7.9

Energy of Chemical Reactions

265

Heat, Work, and the First Law of Thermodynamics 267 Heats of Reaction

270

Thermochemical Equations Hess’s Law

275

277

Standard Heats of Reaction 283

Tools for Problem Solving 293 Review Questions and Problems 295

Bringing It Together: Chapters 5–7

303

8 | The Quantum Mechanical Atom 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10

305

Electromagnetic Radiation 306 Line Spectra and the Rydberg Equation 314 The Bohr Theory 316 The Wave Mechanical Model

318

Quantum Numbers of Electrons in Atoms 324 Electron Spin

326

Energy Levels and Ground State Electron Configurations 328 Periodic Table and Ground State Electron Configurations 330 Atomic Orbitals: Shapes and Orientations

337

Periodic Table and Properties of the Elements 340

Tools for Problem Solving 351 Review Questions and Problems 351

9 | The Basics of Chemical Bonding 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9

Energy Requirements for Bond Formation Ionic Bonding

358

358

Electron Configurations of Ions 362 Lewis Symbols: Keeping Track of Valence Electrons 366 Covalent Bonds

368

Covalent Compounds of Carbon

373

Bond Polarity and Electronegativity 377 Lewis Structures 382 Resonance Structures 394

Tools for Problem Solving

400

Review Questions and Problems

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357

401

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xii | Contents

10 | Theories of Bonding and Structure 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 10.10

408

Five Basic Molecular Geometries 409 Molecular Shapes and the VSEPR Model 411 Molecular Structure and Dipole Moments 420 Valence Bond Theory 424 Hybrid Orbitals and Molecular Geometry 427 Hybrid Orbitals and Multiple Bonds 439 Molecular Orbital Theory Basics 445 Delocalized Molecular Orbitals 452 Bonding in Solids 453

Atomic Size and the Tendency toward Multiple Bond Formation 456 Tools for Problem Solving

462

Review Questions and Problems

464

Bringing It Together: Chapters 8–10

11 | Properties of Gases 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9

470

472

A Molecular Look at Gases 473 Measurement of Pressure 474 Gas Laws 480 Stoichiometry Using Gas Volumes 486 Ideal Gas Law 490 Dalton’s Law of Partial Pressures 499 Kinetic Molecular Theory Real Gases

509

513

Chemistry of the Atmosphere

Tools for Problem Solving

515

519

Review Questions and Problems 521

12 | Intermolecular Attractions and the

Properties of Liquids and Solids 12.1 12.2 12.3 12.4

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527

Gases, Liquids, and Solids and Intermolecular Distances

528

Types of Intermolecular Forces 529 Intermolecular Forces and Properties of Liquids and Solids 537 Changes of State and Dynamic Equilibria 542

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Contents | xiii

12.5 12.6 12.7 12.8 12.9 12.10 12.11 12.12 12.13

Vapor Pressures of Liquids and Solids

544

Boiling Points of Liquids 546 Energy and Changes of State 548 Determining Heats of Vaporization 552 Le Châtelier’s Principle and State Changes Phase Diagrams

555

556

Structures of Crystalline Solids 560 X-Ray Diffraction of Solids 568 Crystal Types and Physical Properties

671

Tools for Problem Solving 576 Review Questions and Problems 577

13 | Mixtures at the Molecular Level:

Properties of Solutions 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8

585

Intermolecular Forces and the Formation of Solutions 586 Heats of Solution 589 Solubility as a Function of Temperature 593 Henry’s Law

595

Temperature-Independent Concentration Units

597

Temperature-Dependent Concentration Units 602 Colligative Properties

603

Heterogeneous Mixtures

Tools for Problem Solving

623

627

Review Questions and Problems 628

Bringing It Together: Chapters 11–13

14 | Chemical Kinetics 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9

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634

636

Factors that Affect Reaction Rates 637 Measuring Reaction Rates Rate Laws

639

645

Integrated Rate Laws

654

Molecular Basis of Collision Theory

664

Molecular Basis of Transition State Theory Activation Energies

667

669

Mechanisms of Reactions 675 Catalysts 680

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xiv | Contents Tools for Problem Solving

684

Review Questions and Problems 686

15 | Chemical Equilibrium 15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8

695

Dynamic Equilibrium in Chemical Systems 696 Equilibrium Laws 698 Equilibrium Laws Based on Pressures or Concentrations 703 Equilibrium Laws for Heterogeneous Reactions 706 Position of Equilibrium and the Equilibrium Constant 708 Equilibrium and Le Châtelier’s Principle

710

Calculating Equilibrium Constants 715 Using Equilibrium Constants to Calculate Concentrations 719

Tools for Problem Solving

731

Review Questions and Problems

733

16 | Acids and Bases, A Molecular Look 16.1 16.2 16.3 16.4 16.5 16.6

740

Brønsted–Lowry Definition of Acids and Bases 741 Strengths of Brønsted–Lowry Acids and Bases 746 Periodic Trends in the Strengths of Acids 750 Lewis Definition of Acids and Bases 755 Acid–Base Properties of Elements and Their Oxides 759 Advanced Ceramics and Acid–Base Chemistry 762

Tools for Problem Solving

766

Review Questions and Problems

767

Bringing It Together: Chapters 14–16 771

17 | Acid–Base Equilibria in Aqueous

Solutions 17.1 17.2 17.3 17.4 17.5 17.6 17.7

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773

Water, pH and “p” notation 774 pH of Strong Acid and Base Solutions 778 Ionization Constants, Ka and Kb 780 Determining Ka and Kb Values

784

pH of Weak Acid and Weak Base Solutions 788 pH of Salt Solutions Buffer Solutions

793

798

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Contents | xv

17.8 Polyprotic Acids 805 17.9 Acid–Base Titrations

811

Tools for Problem Solving 821 Review Questions and Problems

...